Bioactive interpenetrating hybrids of poly(hydroxyethyl methacrylate-co-glycidyl methacrylate): Effect of polysaccharide types on structural peculiarities and multifunctionality.

Crosslinked poly(hydroxyethyl methacrylate-co-glycidyl methacrylate) hybrids prepared in the same experimental condition by adding various polysaccharides of different chemical types; inulin, Na-alginate, starch and κ-Carrageenan were qualitatively compared. The results are presented to extract relevant physicochemical properties for qualitative comparison of structures within the same synthesis batch. Elastic properties and swelling degree of hybrids can be tightly regulated using different types of polysaccharides and by controlling effective cross-linking density. Addition of κ-Carrageenan to copolymer network increased elastic modulus by 6.2-fold in as-prepared state, but greatest increase in effective cross-link density through swelling was observed in alginate-doped gels. An overshooting effect was observed for alginate-doped hybrids; swelling first to a maximum, followed by a gradual deswelling until equilibrium was reached. Compressive elasticity of hybrids is mainly controlled by type of polysaccharides and cross-linking density but also depends on polymerization temperature. The obtained hybrid gels displayed excellent adsorption performance for methyl orange (MO). The highest adsorption capacity was reached with inulin-doped hybrids. The rate of adsorption was very fast and reached equilibrium with 98.9 % efficiency at about 90 min. This approach to modify the properties of hybrid gels with various types of polysaccharides may find wide use in biomaterials and water purification applications.

Structure-property relationships of epoxy functionalized enoate ester-based tailored hybrid gels doped with different polysaccharides.

Natural polymer-based cryogenically structured hybrid gels as support matrices were prepared by constructing synergistic multiple interactions among copolymer poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) and different polysaccharides; hyaluronic acid (HyA), dextrin (Dex), maltodextrin (MDex), carboxymethyl cellulose (CMC) and xanthan gum (XG). Great improvement in thermal stability was achieved in the presence of CMC and MDex. In the as-prepared state, the highest modulus is observed in HyA-doped hydrogels, while in the swollen-state, CMC-doped hydrogels have a greater modulus. Hybrid cryogels showed higher swelling than hybrid hydrogels in all cases, while maximum swelling was obtained in HyA-doped hybrid cryogels. Solvent selection methodology based on solvent/polymer interaction was presented using 16 solvents with various solubility parameters. The PHG/XG network exhibited a more gradual swelling, whereas water uptake of hybrids doped with Dex and MDex were more pronounced dependent on temperature. The adsorption capacity of hybrid cryogels for methyl orange (MO) is both higher and faster compared to hydrogels, while a decrease in the adsorption capacity of hybrid cryogels at equilibrium was observed in the order of MDex > Dex > XG > CMC > HyA. This study provides a perspective on cryogenically structured hybrid material design by comparatively presenting the effectiveness of different polysaccharides that can be used for MO adsorption in water purification assemblies.

Dynamic modulation and epoxy functionalization of protein-mediated enoate ester-based hybrid cryogels.

The current work is focused on the preparation of protein-mediated poly(hydroxyethyl methacrylate-co-glycidyl methacrylate) copolymer as a self-template for in situ synthesis of hybrid gels. Gelatin, collagen, biotin, and l-arginine were used to create hybrid materials with adjustable swelling and elastic properties. Hybrid cryogels tended to swell more than hybrid hydrogels due to their porous nature. Collaged-doped cryogels had the highest swelling, whereas gelatin-doped hybrids showed enhanced elastic modulus. All hybrid gels exhibited pH-sensitive swelling to controlled release applications depending on the degree of protonation of NH2 and COOH groups in the side chains. At low pH conditions, hybrid cryogels exhibited a higher swelling tendency compared to hydrogels. Ion-stimulus-response of hybrid gels was studied to evaluate the effect of salt concentration and features of ambient ions on swelling. Depending on the polyelectrolytic or polyampholytic nature, the extent of swelling in NaCl and KCl solutions varied according to the charge distribution in the network chains. Hybrid gels showed excellent adsorption performance for methyl orange by the presence of epoxy, hydroxyl groups, amino and carboxyl groups providing sufficient active sites. Adsorption capacity of hybrid cryogels is higher than that of hydrogels. The removal rate 97/%, reached an equilibrium state in a short period, suggested that collagen-doped hybrid cryogels have a potential application to remove dyestuff from wastewater. In relation to the decrease of methyl orange concentration in solution, adsorption process followed pseudo-second-order kinetic model. Avrami model has provided a better experimental-calculated fit and adsorption thermodynamics analysis indicated that the adsorption was a spontaneous process with a negative standard free energy. The characteristic findings from this research will provide insights into the design and application of enoate-ester and protein-based combinations in the food, biomedical and cosmetic fields.